1. Photoinduced electron transfers from porphyrin (at the interface) to various type of viologen (as an acceptor) were investigated by the use of molecular assemblies such as a synthetic bilayer which provided a water-organic interface. In case of reactions at a positively charged bilayer, the yield of photoreduced viologen increased in the application of External Magnetic Field, when negatively charged viologen was used as an electron acceptor. This suggested that the radical pair kept a certain distance in the reaction time, and an electron spin-spin interaction remained. On the other hand, the positively charged viologen rapidly left away from the surface of the bilayer after the electron transfer, and a magnetic field effect was not observed.2. The photoinduced electron transfer from the amphiphilic porphyrin to the water soluble viologen in the AOT reversed micelles was investigated with External Magnetic Field Effect. The result clearly showed that the AOT micro-water pool gave a special microenvironment such as a "Cage" in the radical reactions and that the pseudo-linked system was observed.3. The biphotonic ionization of amphiphilic donor compound on the surface of AOT reversed micelles was also studied. The ionization efficiency was controlled by the size of the water pool. The Electron Spin Echo study also showed that the geometry of the donor position on the water-organic interface was controlled by the microenvironment of the micelles such as water pool size.逆ミセル上に担持したポルフィリンから逆ミセル内の微小水滴上のビオロ-ゲンへの光誘起電子移動移動について、外部磁場効果を用いて検討を行った結果、これまで電子供与体ー電子受容体の連結系でしか得られていなかった外部磁場効果が顕著に現れた。その詳しい解析の結果、逆ミセルが擬似連結系となるためのケ-ジの役割を果していることが明かとなった。一方、AOT逆ミセル界面上に担持した両親媒性ドナ-は、紫外光励起で容易に2光子イオン化する事がわかった。このイオン化は、微小水滴内の水の状態によって変化する事が示された。又、これによって生じたラジカルイオンのAOT逆ミセル上の配置について、電子スピンエコ-法よって検討した。その結果、ドナ-部位と親水部との間のメチレン鎖長によって逆ミセル上のドナ-の配置が制御できることが判明した。